CN101824163A - The preparation method of synergistic stabilizer mixture - Google Patents
The preparation method of synergistic stabilizer mixture Download PDFInfo
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- CN101824163A CN101824163A CN201010157779A CN201010157779A CN101824163A CN 101824163 A CN101824163 A CN 101824163A CN 201010157779 A CN201010157779 A CN 201010157779A CN 201010157779 A CN201010157779 A CN 201010157779A CN 101824163 A CN101824163 A CN 101824163A
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Abstract
The present invention describes and a kind ofly is used for preparation and contains following general formula (I), (II) and (III) method of the synergistic stabilizer mixture of component, described mixture comprises the compound that mark is 65-95 weight % (I), mark is the compound (II) of 5 to 35 weight %, and mark is the compound (III) of 0 to 10 weight %
It is characterized by, in phase transfer reaction, the compound of formula V
Epihalohydrin reaction with formula (VI)
Description
It is dividing an application of 03802199.4 original Chinese patent application that the application of this division is based on application number.
Technical field
The present invention relates to a kind of method that is used to prepare based on the synergistic stabilizer mixture of many alkyl-1-oxa-diaza spiro decane compound.
Prior art
Well-known organic materials can be owing to light, radiation, heat or oxygen damage.
At present existing many documents disclose and have been used for the organic materials compound of light and heat effect stabilization relatively.Wherein some document relates to based on 2,2,6, the compound of 6-tetraalkyl piperidines.For effective protection is provided, these stablizers must exist with enough concentration, particularly in the exposure portion of organic materials.
2,2,6, the lower molecular weight representative of 6-tetraalkyl piperidines has the advantage of fast transferring to the sex position that suffers damage especially, and they represent its protective effect at this position.Yet they also have shortcoming, and promptly its volatility is too high and be easy to extract from organic materials.
Though the representative of the higher molecular weight of this compounds also is not easy to extraction, and the slower shortcoming of migration is arranged.In this area, this problem is often by using a kind of mixture of being made up of low (fast transferring) molecular weight stabilizer and high (slowly migration) molecular weight stabilizer to solve.
Therefore, known have quite a large amount of stabilizer blends based on sterically hindered amines, and they do not have or do not have fully above-mentioned shortcoming to a great extent.
As representative example, can mention the mixture described in for example following document: US4,692,486, US4,863,981, US4,957,953, US5,980,783, WO92/12201, WO94/22946, EP449685A, EP623092A, GB2267499A, and ResearchDisclosure No.34549 (in January, 1993).
However, to giving the light stability that organic materials improves or novel, the more virtuous stabilizer blend of use properties very high demand is arranged always.
US6,174,940 disclose following general formula (I), (II) and the synergistic stabilizer mixture (III) based on many alkyl-1-oxa-diaza spiro decane compound, wherein compound (I) is to exist with mark 65-95 weight %, be preferably 75 to 94 weight %, 85 to 94 weight % particularly, the mark of compound (II) is 5 to 35 weight %, be preferably 5 to 20 weight %, 5 to 12 weight % particularly, the mark of compound (III) then is 0 to 10 weight %, is preferably 1 to 5 weight %, 1 to 3 weight % particularly
Wherein
N and m represent 0 to 100 number independently of each other, but both can not be 0,
R
1Expression hydrogen, C
5-C
7Cycloalkyl or C
1-C
12Alkyl,
R
2And R
3Represent hydrogen atom independently of each other, C
1-C
18Alkyl, or constitute 5 to 13 yuan of rings with the carbon atom that connects them is perhaps with the group of the carbon atom constitutional formula (IV) that they are bonded together
R
4And R
5Represent hydrogen or C independently of each other
1-C
22Alkyl, oxyradical O
*,-OH ,-NO ,-CH
2CN, benzyl, allyl group, C
1-C
30Alkoxyl group, C
5-C
12Cycloalkyloxy, C
6-C
10Aryloxy (wherein aryl also can further be substituted), C
7-C
20Alkoxy aryl (wherein aryl also can further be substituted), C
3-C
10Alkenyl, C
3-C
6Alkynyl, C
1-C
10Acyl group, halogen or the phenyl that is unsubstituted or through C
1-C
4The phenyl that alkyl replaces.
Similarly, the preparation of each component of this mixture also has been disclosed in US6, and 174,940, perhaps at this point can be with reference to publication EP 705 836A, EP690 060A and EP 057 885A.
At US6, in 174,940, disclosed mixture be by will component (I), (II) and suitably also have (III) to prepare under the situation in required ratio combination.
For example, this operation can be carried out in powder blenders, and these materials are to mix with dried forms in this mixing tank.Extraly or selectively, this powdered mixture can be by fusion homogenizing, under nitrogen, carry out in case of necessity.This married operation also can carry out by means of solvent, and this solvent is removed by evaporation after forming solution in these components homogenizing again.
This step that is used to prepare component (I), (II) and mixture (III) has its conclusive shortcoming, promptly time-consuming, complicated and expensive, because each other component must prepare at first separately, then, must be in the operation of another physical process with synergitic mixed accurately.
Summary of the invention
Be surprisingly found out that at present component (I), (II) and mixture (III) can pass through reactive mode in-situ preparing cleverly, that is to say, no other physical process operation.
Therefore, the invention provides and a kind ofly be used for preparation and contain general formula (I), (II) and (III) novel method of the Synergistic mixture of component, wherein, it is 65-95 weight % that this mixture comprises mark, be preferably 75 to 94 weight %, the compound of 85 to 94 weight % (I) particularly, mark is 5 to 35 weight %, be preferably 5 to 20 weight %, the particularly compound of 5 to 12 weight % (II), and mark is 0 to 10 weight %, is preferably 1 to 5 weight %, the compound of 1 to 3 weight % (III) particularly
Wherein
N and m represent 0 to 100 number independently of each other, but both can not be 0,
R
1Expression hydrogen, C
5-C
7Cycloalkyl or C
1-C
12Alkyl,
R
2And R
3Represent hydrogen atom independently of each other, C
1-C
18Alkyl, or constitute 5 to 13 yuan of rings with the carbon atom that connects them perhaps constitutes group suc as formula (IV) with the carbon atom that they are bonded together,
And wherein
R
4And R
5Represent hydrogen or C independently of each other
1-C
22Alkyl, oxyradical O
*,-OH ,-NO ,-CH
2CN, benzyl, allyl group, C
1-C
30Alkoxyl group, C
5-C
12Cycloalkyloxy, C
6-C
10Aryloxy (wherein aryl also can further be substituted), C
7-C
20Alkoxy aryl (wherein aryl also can further be substituted), C
3-C
10Alkenyl, C
3-C
6Alkynyl, C
1-C
10Acyl group, halogen or the phenyl that is unsubstituted or through C
1-C
4The phenyl that alkyl replaces.
In the preferred mixture
N and m represent 0 to 10 number independently of each other, but both can not be 0,
R
1Expression hydrogen, C
6Cycloalkyl or C
1-C
4Alkyl,
R
2And R
3Represent hydrogen atom independently of each other, C
1-C
18Alkyl, or constitute 6 to 12 yuan of rings with the carbon atom that connects them perhaps constitutes group suc as formula (IV) with the carbon atom that they are bonded together,
R
4And R
5Represent hydrogen or C independently of each other
1-C
5Alkyl, oxyradical O
*,-OH ,-NO ,-CH
2CN, benzyl, allyl group, C
1-C
10Alkoxyl group, C
5-C
6Cycloalkyloxy, C
6-C
7Aryloxy (wherein aryl also can further be substituted), C
7-C
10Aralkoxy (wherein aryl also can further be substituted), C
3-C
6Alkenyl, C
3-C
6Alkynyl, C
1-C
4Acyl group, halogen or the phenyl that is unsubstituted or through C
1-C
2The phenyl that alkyl replaces.
In the particularly preferred mixture
N and m represent 0 to 5 number independently of each other, but both can not be 0,
R
1The expression methyl,
R
2And R
3Constitute 12 yuan of rings with the carbon atom that connects them, perhaps constitute group suc as formula (IV) with the carbon atom that they are bonded together, and
R
4And R
5Represent hydrogen, methyl, ethanoyl, octyloxy or cyclohexyloxy independently of each other.
Component (I), (II) and Synergistic mixture (III) will be by leading to the compound of formula V
(R wherein
1, R
2, R
3And R
4As defined above, and R
6 -(V) in the expression periodic table of elements (PTE), (VI) or (VII) negatively charged ion of the protonic acid of main group are preferably derived from (VII) main group of PTE), with the epihalohydrin reaction of following formula (VI) and make,
Wherein X represents halogen atom, particularly chlorine, bromine or iodine atom.
For example, derived from (V) among the PTE and (VI) negatively charged ion of the protonic acid of main group be the negatively charged ion of oxygen acid, for example bisulfate ion, sulfate radical, nitrate radical, hydrogen phosphate and phosphate radical.Negatively charged ion derived from the protonic acid of (VII) main group among the PTE for example has fluorion, chlorion, bromide anion and iodide ion, preferred especially cl anion.
With compound (V) and (VI) in the presence of phase-transfer catalyst in inert organic solvents with 1: 1 to 1: 2.9 mol ratio pre-mixing.Then, in the presence of the alkali metal hydroxide of 4 to 20 times of molar weights (with respect to the molar weight of formula V compound), in organic solvent, use phase-transfer catalyst that this premixture reaction is generated required component (I), (II) and Synergistic mixture (III).
Alkali metal hydroxide can solid form uses or is that the aqueous solution form of 9: 1 to 1: 9 (umber of water is to the umber of alkali metal hydroxide) is used as having weight ratio.
The compound of suitable formula V has:
2-sec.-propyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-butyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-isobutyl--7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-amyl group-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-hexyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-heptyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-different heptyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-iso-octyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-nonyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-different nonyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-phenyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-(4-chloro-phenyl-)-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2-dimethyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-ethyl-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-propyl group-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-sec.-propyl-6,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-butyl-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-isobutyl--2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-amyl group-6,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-hexyl-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-nonyl-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2-diethyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2-dipropyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2-dibutyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2-ethyl-2-amyl group-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2-dibenzyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane,
2,2,4,4-tetramethyl--7-oxa--3,12-diaza-14-oxo two spiral shells [5.1.4.2] tetradecane,
2,2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo two spiral shells [5.1.11.2] heneicosane,
2,2,4,4-tetramethyl--7-oxa--3,14-diaza-15-oxo two spiral shells [5.5.5.2] pentadecane,
2,2,4,4,10,10,12,12-prestox-7-oxa--3,11,14-three azepines-15-oxo two spiral shells [5.1.5.2] pentadecane,
2-ethyl-2,7,7,9,9-pentamethyl--1-oxa--3,8-diaza-4-oxo-8--oxyl spiral shell [4.5] decane.
Negatively charged ion R
6 -As hereinbefore defined, be derived from (V) among the PTE, (VI) or (VII) negatively charged ion of the protonic acid of main group, preferably, be preferably chlorion especially derived from (VII) main group of PTE.
As many alkyl oxa-dioxo spiro decane of starting product is known in principle, and can be according to US4, the indication that provides in 110,334 and US4,107,139 and obtaining.
Preferred especially 2,2,4 in compound (V), 4-tetramethyl--7-oxa--3,20-diaza-21-oxo two spiral shells [5.1.11.2] heneicosane hydrochloride.
The epihalohydrin of preferred formula (VI) is an Epicholorohydrin.
The compound of formula V and formula (VI) is with mol ratio 1: 1 to 1: 2.9, and preferred 1: 1 to 1: 2.7, particularly reaction in 1: 2 to 1: 2.5.
This alkali metal hydroxide that is reflected at 4-20 times of molar weight (with respect to the compound of formula V) exists down, in inert organic solvents, carry out, this alkali metal hydroxide is with the solid alkali metal hydroxide form, or with the alkali metal hydroxide aqueous solution form of respective amount, the weight ratio of this aqueous solution is 9: 1 to 1: 9, preferred 2: 3 to 4: 1, particularly 1: 1 to 7: 3 (umber of alkali metal hydroxide is to the umber of water).
Temperature of reaction is preferably 40 to 120 ℃ in 20 to 220 ℃ of scopes, particularly 60 to 90 ℃.
For example, preferred inert organic solvents is aliphatic series or aromatic hydrocarbon, for example sherwood oil, hexane, heptane, petroleum cuts, toluene, hexanaphthene, 1 or dimethylbenzene.Special aromatic hydrocarbons, particularly dimethylbenzene.
Inert organic solvents preferably with weight ratio 2: 1 to 1: 5, more preferably 2: 1 to 1: 3, particularly 2: 1 to 1: 2, with respect to compound (V), and uses.
Used phase-transfer catalyst is a polyoxyethylene glycol, preferably has the polyoxyethylene glycol of average oligomeric degree, particularly Macrogol 200, and its quantitative ratio is 1.5 to 10 weight %, preferred 3 to 7 weight %, particularly 4-6 weight % are with respect to the amount of the compound of used formula V.
Reaction generally finished after 30 to 60 minutes.
After the reaction, excessive epihalohydrin is preferably removed from reaction mixture by distillation.During removing epihalohydrin, the inert organic solvents of some or all also may be removed, and in the case, must supply inert organic solvents with appropriate amount before being separated.
Separate organic phase and water; Wash organic phase with water, preferably remove inert organic solvents again by distillation.
The thickness premixture of gained need not further purification step, can be by at 100 to 240 ℃, and preferably at 120-220 ℃, particularly 150-200 ℃ of heating down preferably under reduced pressure, changes into required formula (I), (II) and mixture (III).
The amount of the amount of the amount by changing used formula V compound, the amount of epihalohydrin (VI), used alkali metal hydroxide and used polyoxyethylene glycol phase-transfer catalyst can change the composition of component (I), (II) and mixture (III) in wide region.
The composition of this mixture (component (I), (II) and (III)) can by conventional spectrography (IR and
13C-NMR spectrum) show.
After the polymerization, this reaction mixture can be optionally by known method at R
4Derived on the position.
Formula (I), (II) and mixture (III) by the inventive method preparation are suitable as the photostabilizer in the following organic materials of listing for example.
1. the polymkeric substance of monoolefine and diolefine, for example polypropylene, polyisobutene, polybutene, poly-but-1-ene, poly--4-methylpent-1-alkene, polyisoprene or polyhutadiene also have the polymkeric substance of cycloolefin, as the polymkeric substance of cyclopentenes or norbornylene; Polyethylene (can optionally be crosslinked) is arranged in addition, as polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), the branched low density polyethylene (BLDPE) of polyethylene (HDPE-HMW), high-density and the ultra-high molar mass of high density polyethylene(HDPE) (HDPE), high-density and high molecular weight.
Polyolefine, promptly as the monoolefine polymer that leading portion exemplified, particularly polyethylene and polypropylene, it can pass through the whole bag of tricks, especially prepares by following method:
A) Raolical polymerizable (normally under high pressure and high temperature)
B) use the catalytic polymerization of the catalyzer of one or more metals comprise IVb, Vb, VIb or VIII family usually.These metals have one or more parts usually, as oxide compound, halogenide, alcoholate, ester, ether, amine, alkyl, alkenyl and/or aryl (it can π-or σ-coordination).These metal complexess can free forms or are fixed on the base material (as activatory magnesium chloride, titanium chloride (III), aluminum oxide or silicon-dioxide).These catalyzer can be to dissolve in or be insoluble in the polymerisation medium.These catalyzer can be as being active in the polyreaction, perhaps can use other activator, belong to Wan Ji oxane as metal alkyls, metal hydride, alkyl metal halide, alkyl metal oxide, for example or Jin, described metal is the element of periodictable Ia, IIa and/or IIIa family.For example, activator can be modified with other ester, ether, amine or silyl ether.These catalyst systems are commonly referred to the Phillips catalyzer, Standard Oil Indiana catalyzer, Ziegler (Natta) catalyzer, TNZ (Du Pont) catalyzer, metallocene catalyst or single site catalysts (SSC).
2. 1) in mentioned mixture of polymers, the mixture of polypropylene and polyisobutene for example, the mixture of polyethylene and polyisobutene, polypropylene and poly mixture (as PP/PE-HD/PE-LD), and dissimilar polyethylene mixture (as PE-LD/PE-HD) to each other.
3. monoolefine and diolefine multipolymer to each other, or the multipolymer of they and other vinyl monomers, ethylene-propylene copolymer for example, the mixture of linear low density polyethylene (PE-LLD) and itself and new LDPE (film grade) (PE-LD), propylene-but-1-ene multipolymer, propylene-isobutylene copolymers, ethene-but-1-ene multipolymer, ethene-hexene copolymer, ethene-methylpentene multipolymer, ethene-heptene multipolymer, ethylene-octene copolymer, propylene-butadienecopolymer, isobutylene-isoprene copolymer, ethylene-acrylic acid alkyl ester copolymer, the ethylene-methyl methacrylate alkyl ester copolymer, the multipolymer of ethylene-vinyl acetate copolymer and they and carbon monoxide, or ethylene-acrylic acid copolymer and their salt (ionomer), also have ethene and propylene and diene such as hexadiene, the terpolymer of Dicyclopentadiene (DCPD) or ethylidene norbornene; And this analog copolymer mixture to each other, with they and 1) in mentioned mixture of polymers, for example polypropylene-ethylene-propylene copolymer, PE-LD-ethylene-vinyl acetate copolymer, PE-LD-ethylene-acrylic acid copolymer, PE-LLD-ethylene-vinyl acetate copolymer, PE-LLD-ethylene-acrylic acid copolymer, and the mixture of block or random poly-alkylene-carbon monoxide multipolymer and they and other polymkeric substance such as polymeric amide.
4. hydrocarbon resin is (as C
5-C
9), comprise their the hydrogenation variant (as tackifier resins) and the mixture of poly-alkylene and starch.
5. polystyrene, poly-(p-methylstyrene), poly-(alpha-methyl styrene).
6. the multipolymer of vinylbenzene or alpha-methyl styrene and diene or acrylic acid series derivative, for example styrene butadiene, styrene-acrylonitrile, vinylbenzene-alkyl methacrylate, styrene butadiene-alkyl acrylate, styrene butadiene-alkyl methacrylate, phenylethylene-maleic anhydride, styrene-acrylonitrile-methacrylic ester; The mixture of high impact strength of styrene multipolymer and another kind of polymkeric substance (as polyacrylic ester, diene polymer or ethylene-propylene-diene terpolymer); And cinnamic segmented copolymer, as styrene-butadiene-styrene, styrene-isoprene-phenylethene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.
7. the graft copolymer of vinylbenzene or alpha-methyl styrene, for example styrene-grafted on the polyhutadiene, styrene-grafted on Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, vinylbenzene and vinyl cyanide (methacrylonitrile) be grafted on the polyhutadiene; Vinylbenzene, vinyl cyanide and methyl methacrylate-grafted are on polyhutadiene; Vinylbenzene and maleic anhydride graft are on polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide are grafted on the polyhutadiene; Vinylbenzene and maleimide are grafted on the polyhutadiene; Vinylbenzene and alkyl acrylate or alkyl methacrylate are grafted on the polyhutadiene, vinylbenzene and acrylonitrile grafting are on ethylene-propylene-diene terpolymer, vinylbenzene and acrylonitrile grafting are on polyalkyl acrylate or polyalkyl methacrylate, vinylbenzene and acrylonitrile grafting are on acrylate-butadienecopolymer, and they and 6) in the mixture of mentioned multipolymer, as the known copolymer mixture that is called ABS, MBS, ASA or AES polymkeric substance.
8. polymer containing halogen, as the chlorination of sovprene, chlorinated rubber, isobutylene-isoprene and multipolymer, Epicholorohydrin homopolymer and the multipolymer of brominated copolymer (halogenated butyl rubber), chlorination or sulfo group chlorinatedpolyethylene, ethene and ethylene chloride, the polymkeric substance of halogen-containing vinyl compound particularly is as polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride); And their multipolymer, as vinylchlorid-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
9. derived from alpha, the polymkeric substance of beta-unsaturated acid and derivative thereof is as polyacrylic ester and polymethacrylate, polyacrylonitrile, polyacrylamide with through the impact-resistant modified polymethylmethacrylate of butyl acrylate.
10. 9) in mentioned monomer to each other or with the multipolymer of other unsaturated monomers, as acrylonitrile butadiene copolymer, vinyl cyanide-alkyl acrylate copolymer, vinyl cyanide-alkoxyalkyl acrylate multipolymer, vinyl cyanide-halogen ethylene copolymer or vinyl cyanide-alkyl methacrylate-butadiene terpolymer.
11. derived from unsaturated alkohol and amine or the acyl derivative or the polymkeric substance of their acetal, for example polyvinyl alcohol, polyvinyl acetate (PVA), polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral acetal, poly-O-phthalic allyl propionate or polyene propyl group trimeric cyanamide; And the multipolymer of the alkene of mentioning in they and the part 1.
12. the homopolymer of cyclic ether and multipolymer are as the multipolymer of polyalkylene glycol, polyoxyethylene, polyoxytrimethylene or they and bisglycidyl ether.
13. polyacetal, as polyoxymethylene, and those contain the polyoxymethylene of common monomer such as ethylene oxide; Polyacetal through thermoplastic polyurethane, acrylate or MBS modification.
14. polyphenylene oxide and polyphenylene sulfide, and the mixture of they and styrene polymer or polymeric amide.
15. be end hydroxy polyether, polyester and polyhutadiene and be the urethane of aliphatic series or aromatic polyisocyanate on the other hand, and their precursor derived from one side.
16. derived from diamines and dicarboxylic acid and/or derived from the polymeric amide and the copolyamide of aminocarboxylic acid or corresponding lactam, for example polymeric amide 4,6, and 6/6,6/10,6/9,6/12,4/6,12/12,11 and 12; Between originating in-aromatic poly of dimethylbenzene, diamines and hexanodioic acid; From hexanediamine and m-phthalic acid and/or terephthalic acid preparation and have or do not have the polymeric amide of elastomerics as properties-correcting agent, as poly--2,4,4-trimethylammonium hexylidene terephthalamide or poly.Aforesaid polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding elastomerics or the elastomeric segmented copolymer of grafting; Or the segmented copolymer of aforesaid polymeric amide and polyethers such as polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol.In addition, through polymeric amide or copolyamide with EPDM or ABS modification; And the polymeric amide of condensation during processing (RIM polymeric amide system).
17. polyureas, polyimide, polyamide-imide, polyetherimide, polyesteramide, poly-glycolylurea and polybenzimidazole.
18. polyester derived from dicarboxylic acid and dibasic alcohol and/or hydroxycarboxylic acid or corresponding lactone, as polyethylene terephthalate, polybutylene terephthalate, poly--1,4-hydroxymethyl-cyclohexane terephthalate, poly-hydroxybenzoate, and derived from the block polyether-ester of end hydroxy polyether; Also have through polyester with polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate.
20. polysulfones, polyethersulfone and polyetherketone.
21. derived from one side is aldehyde, and is the cross-linked polymer of phenol, urea or trimeric cyanamide on the other hand, for example phenol/formaldehyde resin, urea/formaldehyde resin and melamine/formaldehyde resin.
22. dry and undried Synolac.
23. derived from saturated and unsaturated dicarboxylic acid and polyvalent alcohol and vinyl compound unsaturated polyester resin, and their halogen-containing variant with low combustible as linking agent.
24. the crosslinkable acrylic derived from the acrylate that is substituted such as epoxy acrylate, urethane acrylate or polyester acrylate is a resin.
25. Synolac, vibrin and acrylic resin with melamine resin, urea resin, isocyanic ester, isocyanuric acid ester, polyisocyanates or cross linking of epoxy resin.
26. cross-linked epoxy resin derived from aliphatic series, cyclic aliphatic, heterocycle system or aromatics glycidyl compound, the product of bisphenol A diglycidyl ether, Bisphenol F diglycidylether for example, for example, they are by the stiffening agent of routine such as acid anhydrides or amine, and use or do not use promotor and crosslinked.
27. natural polymer, as Mierocrystalline cellulose, natural rubber, gelatin, and through the polymer system mode derivative of chemical modification in addition, for example cellulose acetate, cellulose propionate and cellulose butylate, or ether of cellulose such as methylcellulose gum; And rosin and derivative thereof.
28. above-mentioned mixture of polymers (blend polymer), for example PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/BT, PVC/CPE, PVC/ propionic ester system, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ propionic ester, POM/MBS, PPO/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/PE-HD, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. constitute natural and synthetic organic substance or its mixture of pure monomer formulation, example has mineral oil, animal or plant fat, oil and wax, or based on the oil, wax and the fat that synthesize ester (as phthalic ester, adipic acid ester, phosphoric acid ester or trimellitate), and the blend that synthesizes ester and mineral oil with any required part by weight blended, for example those that use as the spin coating finish paint, and water miscible liquid.
30. natural or elastomeric water miscible liquid is as the latex of natural rubber latex or carboxylation of styrene-butadienecopolymer.
Formula (I), (II) and the mixture (III) that makes by the inventive method can directly be used for stablizing above-mentioned organic materials, perhaps with other additives, for example form of the suitable combination of antioxidant, photostabilizer, metal passivator, static inhibitor, fire retardant, lubricant, nucleator, acid scavenger (alkaline co-stabilizer), pigment and filler.
For example, the antioxidant and the photostabilizer that can be used for the formulation of the present invention prepared (I), (II) and mixture (III) extraly is based on sterically hindered amines or the sterically hindered phenol or the compound of the co-stabilizer of sulfur-bearing or phosphorus.The example of the suitable additive of application capable of being combined is as hereinafter listed:
1. antioxidant
1.1 alkylation monohydric phenol, for example 2, the 6-di-tert-butyl-4-methy phenol, 2-butyl-4, the 6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, the 6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol, the nonylphenol of straight or branched, as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(phenol of 1 '-methyl undecane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl heptadecane-1 '-yl), 2,4-dimethyl-6-(1 '-methyl tridecane-1 '-yl) phenol, and their mixture.
1.2 alkylthiomethyl phenol, for example 2,4-dioctyl sulphomethyl-6-tert.-butyl phenol, 2,4-dioctyl sulphomethyl-6-methylphenol, 2,4-dioctyl sulphomethyl-6-ethylphenol, 2,6-two (dodecyl sulphomethyl)-4-nonylphenol.
1.3 quinhydrones and alkylation quinhydrones, for example 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-BHA, 3,5-di-t-butyl-4-BHA, stearic acid-3,5-di-t-butyl-4-hydroxylphenyl ester, two (3, the 5-di-t-butyl-4-hydroxybenzene) esters of hexanodioic acid.
1.4 hydroxylation diphenyl sulfide, for example 2,2 '-thiobis (the 6-tertiary butyl-4-methylphenol), 2,2 '-thiobis (4-octyl phenol), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (the 6-tertiary butyl-2-methylphenol), 4,4 '-thiobis (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxybenzene) disulphide.
1.5 alkylidene bis-phenol, for example 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylidene two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylidene two (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-the 4-nonylphenol], 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl sulfydryl butane of 1-, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Dicyclopentadiene (DCPD), two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-6-tertiary butyl-4-aminomethyl phenyl] esters of terephthalic acid, 1,1-two (3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propane, 2, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-4-dodecyl sulfydryl butane of 2-, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane, ethylene glycol bis [3, two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric esters of 3-].
1.6 O-, N-and S-benzyl compounds, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-dihydroxyl dibenzyl ether, 4-hydroxyl-3,5-dimethyl benzyl mercaptoacetic acid stearyl, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, two (the 4-tertiary butyls-3-hydroxyl-2 of dithio terephthalic acid, the 6-dimethyl benzyl) ester, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide, 3,5-di-tert-butyl-4-hydroxyl benzyl isooctyl thioglycollate, 4-hydroxyl-3,5-di-t-butyl benzyl mercaptoacetic acid tridecyl ester.
1.7 the malonic ester of acrinylization, for example 2, two (3,5-di-t-butyl-2-acrinyl) propanedioic acid two (octadecyl) esters of 2-, 2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) propanedioic acid two (octadecyl) ester, mercaptoethyl-2,2-two (3,5-di-t-butyl-4-acrinyl) propanedioic acid two (dodecyl) ester, 2, [4-(1,1 for propanedioic acid two for 2-two (3,5-di-t-butyl-4-acrinyl), 3, the 3-tetramethyl butyl) phenyl] ester.
1.8 aromatics acrinyl compound, for example 1,3,5-three (3,5-di-t-butyl-4-acrinyl)-2,4,6-Three methyl Benzene, 1, two (3,5-di-t-butyl-4-acrinyl)-2,3 of 4-, 5,6-tetramethyl-benzene, 2,4,6-three (3,5-di-t-butyl-4-acrinyl) phenol.
1.9 triaizine compounds, for example 2, the two octyl group sulfydryl-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 4-; 3, the 5-triazine; 2-octyl group sulfydryl-4, two (3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 6-; 3, the 5-triazine; 2-octyl group sulfydryl-4,6-two (3; 5-di-t-butyl-4-hydroxyphenoxy)-1,3,5-triazines; 2; 4,6-three (3,5-di-t-butyl-4-hydroxyphenoxy)-1; 2, the 3-triazine; 1,3; 5-three (3,5-di-t-butyl-4-acrinyl) isocyanuric acid ester; 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester; 2,4; 6-three (3,5-di-t-butyl-4-leptodactyline)-1,3; the 5-triazine; 1,3,5-three (3; 5-di-tert-butyl-hydroxy phenyl propionyl) six hydrogen-1,3,5-triazines; 1; 3,5-three (3,5-dicyclohexyl-4-acrinyl) isocyanuric acid ester.
1.10 benzylphosphonic acid ester, for example 2,5-di-t-butyl-4-acrinyl dimethyl phosphonate, 3,5-di-t-butyl-4-acrinyl diethyl phosphonate, 3,5-di-t-butyl-4-acrinyl phosphonic acids two (octadecyl) ester, 5-tertiary butyl-4-hydroxy-3-methyl-benzyl phosphonic acids two (octadecyl) ester, 3, the calcium salt of 5-di-t-butyl-4-acrinyl phosphonic mono ethyl ester.
1.11 acyl aminophenols, for example 4-hydroxy-n-lauroyl aniline, 4-hydroxy-n-stearanilide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
1.12 β-(3,5-di-t-butyl-4-hydroxyphenyl) ester of propionic acid and monohydroxy-alcohol or polyvalent alcohol formation, described monohydroxy-alcohol or polyvalent alcohol for example have methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.
1.13 the ester that β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol form, described monohydroxy-alcohol or polyvalent alcohol for example have methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, two (hydroxyethyl) oxamide of N-, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.
1.14 β-(3,5-dicyclohexyl-4-hydroxyphenyl) ester of propionic acid and monohydroxy-alcohol or polyvalent alcohol formation, described monohydroxy-alcohol or polyvalent alcohol for example have methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.
1.153, the ester that 5-di-t-butyl-4-hydroxyphenyl acetic acid and monohydroxy-alcohol or polyvalent alcohol form, described monohydroxy-alcohol or polyvalent alcohol for example have methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.
1.163, the ester that two (3 '-tertiary butyl-4 '-hydroxyphenyl) butyric acid of 3-and monohydroxy-alcohol or polyvalent alcohol form, described monohydroxy-alcohol or polyvalent alcohol for example have methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.
1.17 β-(3; 5-di-t-butyl-4-hydroxyphenyl) acid amides of propionic acid; N for example; N '-two (3; 5-di-t-butyl-4-hydroxyphenyl propionyl) hexanediamine, N, N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) propylene diamine, N; N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) hydrazine.
1.18 tocopherol is as alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and their mixture (vitamin-E).
1.19 the acrinyl aromatic substance, as 1,3,5-three (3,5-di-t-butyl-4-acrinyl)-2,4,6-Three methyl Benzene, 1, two (3,5-di-t-butyl-4-acrinyl)-2,3,5 of 4-, 6-tetramethyl-benzene, 2,4,6-three (3,5-di-t-butyl-4-acrinyl) phenol.
1.20 xitix (vitamins C).
1.21 amine antioxidant, N for example, N '-di-isopropyl-Ursol D, N, N '-two sec-butyls-Ursol D, N, N '-two (1,4-dimethyl amyl group)-Ursol D, N, N '-two (1-ethyl-3-methyl amyl)-Ursol D, N, N '-two (1-methylheptyl)-Ursol D, N, N '-dicyclohexyl-Ursol D, N, N '-phenylbenzene-Ursol D, N, N '-two (the Ursol D of naphthyl-2-), N-sec.-propyl-N '-phenyl-Ursol D, N-(1, the 3-dimethylbutyl)-N '-phenyl-Ursol D, N-(1-methylheptyl)-N '-phenyl-Ursol D, N-cyclohexyl-N '-phenyl-Ursol D, 4-(tolysulfonyl amino) pentanoic, N, N '-dimethyl-N, N '-two sec-butyls-Ursol D, pentanoic, N-allyl group pentanoic, 4-isopropoxy pentanoic, the N-phenyl-1-naphthylamine, N-(uncle's 4-octyl phenyl-naphthalidine, N-phenyl-2-naphthylamines, octylated diphenylamine is (for example right, right '-two uncle's octyl diphenylamine), 4-n-butyl amine base phenol, 4-amide-based small phenol, 4-nonanoyl amino-phenol, 4-dodecanoyl amino-phenol, 4-stearyl amido phenol, two (4-p-methoxy-phenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, N, N, N ', N '-tetramethyl--4,4 '-diaminodiphenyl-methane, 1,2-two [(2-tolyl)-amino] ethane, 1,2-two (phenylamino) propane, (o-tolyl) biguanides, two [4-(1 ', 3 '-dimethylbutyl)-and phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine, the mixture of monoalkylation and the dialkyl group tertiary butyl/uncle's octyl diphenylamine, the mixture of monoalkylation and dialkyl group nonyl diphenylamine, the mixture of monoalkylation and dialkyl group dodecyl diphenylamine, the mixture of monoalkylation and dialkyl group sec.-propyl/isohexyl-pentanoic, the mixture of monoalkylation and dialkyl group tertiary butyl pentanoic, 2,3-dihydro-3,3-dimethyl-4H-1, the 4-benzothiazine, thiodiphenylamine, the mixture of monoalkylation and the dialkyl group tertiary butyl/uncle's octyl group-thiodiphenylamine, the mixture of monoalkylation and dialkyl group uncle octyl group thiodiphenylamine, N-allyl group thiodiphenylamine, N, N, N ', N '-tetraphenyl-1,4-diamino-but-2-ene, N, N-two (2,2,6,6-tetramethyl piperidine-4-yl) hexanediamine, two (2,2,6,6-tetramethyl piperidine-4-yl) sebate, 2,2,6,6-tetramethyl piperidine-4-ketone, 2,2,6,6-tetramethyl piperidine-4-alcohol.
2.UV absorption agent and photostabilizer
(2.12-2 '-hydroxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-[2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole; 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 ' ,-two tert-pentyl-2 '-hydroxy phenyls) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-hydroxy phenyl) benzotriazole; 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl)-phenyl-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl)-phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and the 2-(mixture of 3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different hot oxygen carbonyl ethyl of 2-) phenyl benzotriazole, 2, [4-(1 for 2 '-methylene radical-two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl] ester exchange offspring of benzotriazole and Liquid Macrogol; [R-CH
2CH
2-COO (CH
2)
3]-
2, R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base-phenyl wherein.
2.22-dihydroxy benaophenonel, for example 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivative.
2.3 the benzoic ester that is substituted or is unsubstituted; for example Whitfield's ointment-4-the tertiary butyl-phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol, 3; 5-di-tert-butyl-4-hydroxybenzoic acid-2; 4-di-t-butyl phenyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid stearyl, 3; 5-di-tert-butyl-4-hydroxybenzoic acid-2-methyl-4,6-di-t-butyl phenyl ester.
2.4 acrylate, alpha-cyano-β for example, β-diphenyl-ethyl acrylate or different monooctyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-to methoxyl group-methyl cinnamate or butyl ester, α-methoxycarbonyl-p-methoxycinnamic acid methyl esters, N-(beta-methoxy-carbonyl-β-acrylonitrile base)-2-methyl indoline.
2.5 nickel compound; for example have or do not have 2 of extra ligand such as n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine; [4-(1 for 2 '-thiobis; 1; 3; the 3-tetramethyl butyl) phenol] nickel complex; for example 1: 1 or 1: 2 title complex; nickel dibutyl dithiocarbamate; mono alkyl ester such as 4-hydroxyl-3; the nickel salt of 5-di-t-butyl benzylphosphonic acid methyl esters or ethyl ester, the nickel complex of ketoxime such as 2-hydroxy-4-methyl phenyl undecyl ketoxime has or does not have the nickel complex of the 1-phenyl-4-lauroyl-5-hydroxypyrazoles of extra ligand.
2.7 oxamide, for example 4,4 '-two octyloxies-N-oxanilide, 2,2 '-diethoxy-N-oxanilide, 2,2 '-two octyloxies-5,5 '-di-t-butyl-N-oxanilide, 2,2 '-two (dodecyloxy)-5,5 '-di-t-butyl-N-oxanilide, 2-oxyethyl group-2 '-ethyl-N-oxanilide, N, N '-two (3-dimethylamino-propyl)-oxamide, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl-N-oxanilide and with 2-oxyethyl group-2 '-ethyl-5, the mixture of 4 '-di-t-butyl-N-oxanilide, and O-methoxy-and to the mixture of methoxyl group-two replacement-N-oxanilide and adjacent oxyethyl group-with to the mixture of oxyethyl group-two replacement-N-oxanilide.
(2.82-2-hydroxy phenyl)-1,3,5-triazine, for example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4 ', 6-two (2 ', the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1,3 of 6-, the 5-triazine, 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3 of 4-, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (4-aminomethyl phenyl-the 1,3,5-triazines of 6-, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[4-dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-]-the 2-hydroxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-) phenyl]-1,3, the 5-triazine, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3,5-triazines.
3. metal passivator; N for example; N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicyloyl hydrazine, N; N '-two (salicyloyl) hydrazine, N; N '-two (3; 5-di-t-butyl-4-hydroxyphenyl propionyl) hydrazine, 3-salicylamide base-1; 2; 4-triazole, two (benzal) oxalyl group two hydrazines, N-oxanilide, isophthaloyl two hydrazines, the two phenyl hydrazine of sebacoyl, N; N '-diacetyl adipyl two hydrazines, N; N '-two (salicyloyl) oxalyl group two hydrazines, N, N '-two (salicyloyl) sulfo-propionyl two hydrazines.
4. phosphorous acid ester and phosphinate, triphenyl phosphite for example, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl benzene) ester, trilauryl phosphite, tricresyl phosphite (octadecyl) ester, distearyl pentaerythrityl diphosphite, tricresyl phosphite (2, the 4-di-tert-butyl) ester, the diiso decyl pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two isodecyl oxygen base pentaerythritol diphosphites, two (2,4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphites, three stearyl Sorbitol Powder GW-540s, 4,4 '-biphenylene, two phosphonous acid four (2, the 4-di-tert-butyl-phenyl) ester, 6-different octyloxy-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-dioxane phosphorous acid ester (phosphocin), 6-fluoro-2,4,8,10-tetra-tert-12-methyl-dibenzo [d, g]-1,3,2-dioxane phosphorous acid ester, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) methyl esters, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) ethyl ester, tricresyl phosphite (the 2-tertiary butyl-4-sulfo--(2 '-methyne-4 '-hydroxyl-the 5 '-tertiary butyl) phenyl-5-methyne) phenyl ester, 2,2 '; 2 "-nitrilo [three (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) triethyl-phosphite], two [2-methyl-4, two (1, the 1-dimethyl ethyl) phenol of 6-] the phosphorous acid ethyl ester.
5. oxyamine, N for example, N-dibenzyl oxyamine, N, N-diethyl oxyamine, N, N-dioctyl oxyamine, N, N-dilauryl oxyamine, N, N-two (tetradecyl) oxyamine, N, N-two (hexadecyl) oxyamine, N, N-two (octadecyl) oxyamine, N-hexadecyl-N-octadecyl oxyamine, N-heptadecyl-N-octadecyl oxyamine, the N that makes by hydrogenated tallow amine, N-dialkyl group oxyamine.
6. nitrone, for example N-benzyl-alpha-phenyl nitrone, N-ethyl-Alpha-Methyl nitrone, N-octyl group-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, derived from by the prepared N of hydrogenated tallow amine, the nitrone of N-dialkyl group oxyamine.
7. zeolite and hydrotalcite are for example available from the DHT of Kisuma company
4A, available from the Hycithe of S ü dchemie company
713 or available from the Pura1 of Condea company
MG61HT.
This houghite can be described with following formula
[(M
2+)
1-x(M
3+)
x(OH)
2(A
n-)
x/nyH
2O]，
Wherein
(M
2+) expression Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni
(M
3+) expression Al, B, Bi
A
N-The expression valency is the negatively charged ion of n
N represents the integer of 1-4
X represents 0 to 0.5 value
Y represents 0 to 2 value
A represents OH
-, Cl
-, Br
-, I
-, ClO
4-, CH
3COO
-, C
6H
5COO
-, CO
3 2-, SO
4 2-, (OOC-COO)
2-, (CHOHCOO)
2 2-, (CHOH)
4CH
2OHCOO
-, C
2H
4(COO)
2 2-, (CH
2COO)
2 2-, CH
3CHOHCOO
-, SiO
3 2-, SiO
4 4-, Fe (CN)
6 3-, Fe (CN)
6 4-, BO
3 3-, PO
3 3-, HPO
4 2-
Preferred wherein (the M that uses
2+) expression (Ca
2+), (Mg
2+), or (Mg
2+) and (Zn
2+) mixture; (A
N-) expression CO
3 2-, BO
3 3-, PO
3 3-X has the hydrotalcite that 0 to 0.5 value and y have 0 to 2 value.Also can use the hydrotalcite of describing with following formula
[(M
2+)
x(Al
3+)
2(OH)
2x+6nz(A
n-)
2yH
2O]，
Herein, (M
2+) expression Mg
2+, Zn
2+, but Mg more preferably
2+(A
N-) the expression negatively charged ion, particularly be selected from CO
3 2-, (OOC-COO)
2-, OH
-And S
2-, wherein n describes the ionic valency.Y is a positive number, more preferably is 0 to 5, especially 0.5 to 5.X and z all have on the occasion of, wherein x preferably 2 to 6, and z should be less than 2.The hydrotalcite of following formula should be considered as particularly preferred:
Al
2O
3×6MgO×CO
2×12H
2O，
Mg
4.5Al
2(OH)
13×CO
3×3.5H
2O，
4MgO×Al
2O
3×CO
2×9H
2O，
4MgO×Al
2O
3×CO
2×6H
2O，
ZnO×3MgO×Al
2O
3×CO
2×8-9H
2O，
ZnO×3MgO×Al
2O
3×CO
2×5-6H
2O，
Mg
4.5Al
2(OH)
13×CO
3。
Preferably, the working concentration of hydrotalcite in polymkeric substance is 0.01 to 5 weight %, and 0.2 to 3 weight % particularly is based on whole polymkeric substance accent side.
8. sulfo-synergist, for example Tyox B and distearylthiodi-propionate.
9. peroxide scavenger, for example zinc salt of the ester of β-thio-2 acid (as lauryl, stearyl ester, myristin or tridecyl ester), mercaptobenzimidazole, 2-mercaptobenzimidazole, alkyl zinc dithiocarbamate, zinc dibutyl dithiocarbamate, two (octadecyl) monosulphide, two (octadecyl) disulphide, tetramethylolmethane four (β-dodecyl sulfydryl) propionic ester.
10. polymeric amide stablizer, for example combination of the salt of mantoquita and iodide and/or phosphorus compound and bivalent manganese.
11. alkaline co-stabilizer, the for example an alkali metal salt of trimeric cyanamide, Polyvinylpyrolidone (PVP), Dyhard RU 100, triallyl cyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt, for example calcium stearate, Zinic stearas, mountain Yu acid magnesium, Magnesium Stearate, sodium ricinate, potassium palmitate, pyrocatechol antimony or pyrocatechol tin.
12. nucleator, for example inorganic substance, for example talcum, metal oxide, as titanium dioxide or magnesium oxide, phosphoric acid salt, carbonate or vitriol (preferably alkaline earth salt), organic compound is as monobasic or polycarboxylic acid and salt thereof, for example 4-p t butylbenzoic acid, hexanodioic acid; Phenylbenzene acetic acid; Sodium succinate or Sodium Benzoate; The acetal of aromatic aldehyde and polyfunctional alcohol such as Sorbitol Powder, this Sorbitol Powder for example has 1,3-2,4-two (benzal)-D-Sorbitol Powder, 1,3-2,4-two (4-toluene fork)-D-Sorbitol Powder, 1,3-2,4-two (4-ethyl benzal)-D-Sorbitol Powder; Polymerizable compound is as ionic copolymer (ionomer).
13. filler and toughener, for example fiber, the synthon of lime carbonate, silicate, glass fibre, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and metal hydroxides, carbon black, graphite, wood powder and other powder classes or other natural product.
14. other additives, for example softening agent, lubricant, emulsifying agent, pigment, rheologic additive, catalyzer, leveling auxiliary agent, white dyes, fire retardant, static inhibitor, whipping agent.
15. benzofuranone and indoline, for example be described in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102, or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl benzo furans-2-ketone, 5,7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl]-benzofuran-2-ones, 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones, 5,7-di-t-butyl-3-(4-ethoxyl phenenyl benzofuran-2-ones, 3-(4-acetyl oxygen-3, the 5-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(3,5-diethyl-4-new pentane acyloxy phenyl)-5,7-di-t-butyl benzo furans-2-ketone.
Can 0.01 to 10 weight % with the additive of the above various addings of the 1st to 12 group and the 15th group, 0.01 to 5 weight % preferably joins this based on the amount of the gross weight for the treatment of stable organic materials and treats in the stable polymer.The ratio of the additive of the 13rd group and the 14th group then is 0.1 to 80 weight %, 0.1 to 50 weight % preferably, and it is in treating stable organic materials.
Use commonly used and known method is mixed these additives and treated in the stable organic materials.For example, the carrying out of mixing can by be mixed in the good polymkeric substance of firm polymerization or be shaped before or during melt in, or with mixture of the present invention with must leave no choice but that other additive is used to the good polymkeric substance of firm polymerization or before being shaped or during melt in.
The carrying out of mixing also can be by will being applied directly in the polymkeric substance through dissolving or dispersive compound, or by they being mixed into solution, suspension or the emulsion of polymkeric substance, under the suitable situation, and solvent evaporated subsequently.
If these compounds mix in independent procedure of processing in the polymkeric substance of granulation subsequently, also be effective.
Prepared compound also can contain the master batch form of these compounds according to the present invention, is 1 to 75 weight % with concentration for example, and preferably 2.5 to 60 weight % add and treat in the stable polymer.
The important advantage that method of the present invention provides is, when component (I), (II) and mixture (III) can obstructedly be gone to undue expense, complexity and the component that expensively each made mix and prepare, the ground that replaces advantageously and astoundingly is the reactive mode in-situ preparing with dexterity.
Following embodiment is used to illustrate theme of the present invention.
Embodiment 1-6
About the value of described variable x and y, referring to table 1.
In x gram dimethylbenzene, mix 2 of 200.3 grams (0.50 mole) in succession, 2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo two spiral shells [5.1.11.2] heneicosane hydrochloride, 10 gram Macrogol 200s and y gram Epicholorohydrin and 164.0 gram concentration are 50% aqueous sodium hydroxide solution (2.05 moles).
Stirred this mixture 40 minutes down at 70 ℃.After evaporating excessive Epicholorohydrin and xylene solvent, in reaction mixture, add 220g dimethylbenzene and 220g water and phase-splitting.With 110 gram water washing organic phases, wash twice at every turn.Distillation under reduced pressure removes desolvates, and obtains yellow oil, and it need not to be further purified and promptly obtain required mixture reacting under 220 ℃ under vacuum.Product is a kind of crisp, almost colourless resin, and its output, melting range and soltion viscosity are summarized in the table 1.
Table 1
| The embodiment numbering | X (gram) (dimethylbenzene) | Y (gram) (Epicholorohydrin) | Output (gram) | Melting range (℃) | Soltion viscosity (mm 2/s) 1 |
| ??1 | ??345.0 | ??115.6 | ??98.5 | ??158-210 | ??1.83 |
| ??2 | ??114.9 | ??115.6 | ??98.1 | ??166-216 | ??2.23 |
| ??3 | ??172.5 | ??115.6 | ??98.2 | ??163-216 | ??2.09 |
| ??4 | ??241.5 | ??115.6 | ??98.7 | ??160-210 | ??2.00 |
| ??5 | ??345.0 | ??92.5 | ??96.0 | ??153-202 | ??1.64 |
| ??6 | ??345.0 | ??104.1 | ??99.0 | ??146-197 | ??1.75 |
1)According to DIN 51562, under 25 ℃, the toluene solution of 20% concentration
Claims (32)
1. contain following general formula (I), (II) and (III) synergistic stabilizer mixture of component as the purposes of the light stabilizer in the organic material; It is the 65-95 % by weight that described mixture comprises mark; Be preferably 75 to 94 % by weight; The compound of 85 to 94 % by weight (I) particularly; Mark is 5 to 35 % by weight; Be preferably 5 to 20 % by weight; The compound of 5 to 12 % by weight (II) particularly; And mark is 0 to 10 % by weight; Be preferably 1 to 5 % by weight; The compound of 1 to 3 % by weight (III) particularly
Wherein
N and m represent 0 to 100 number independently of each other, but both can not be 0,
R
1Expression hydrogen, C
5-C
7Cycloalkyl or C
1-C
12Alkyl,
R
2And R
3Represent hydrogen atom independently of each other, C
1-C
18Alkyl, or constitute 5 to 13 yuan of rings with the carbon atom that connects them, perhaps with the group of the carbon atom constitutional formula (IV) that they are bonded together,
R
4And R
5Represent hydrogen or C independently of each other
1-C
22Alkyl, oxyradical O
*,-OH ,-NO ,-CH
2CN, benzyl, allyl group, C
1-C
30Alkoxyl group, C
5-C
12Cycloalkyloxy, C
6-C
10Aryloxy (wherein aryl also can further be substituted), C
7-C
20Alkoxy aryl (wherein aryl also can further be substituted), C
3-C
10Alkenyl, C
3-C
6Alkynyl, C
1-C
10Acyl group, halogen or the phenyl that is unsubstituted or through C
1-C
4The phenyl that alkyl replaces,
It is characterized by, in phase transfer reaction, the compound of formula V
, R wherein
1, R
2, R
3And R
4As defined above, and R
6 -The negatively charged ion of expression protonic acid is with the epihalohydrin reaction of formula (VI)
, wherein X represents chlorine, bromine or iodine atom, and then carries out polyreaction to prepare described mixture.
2. according to the purposes of claim 1, it is characterized by following steps: pre-mixing compound (V), (VI) and phase-transfer catalyst in organic solvent, the solid alkali metal oxyhydroxide or the alkali metal hydroxide aqueous solution that add 4-20 times of molar weight (with respect to compound (V)), under 20-220 ℃ temperature, react, remove excessive epihalohydrin (VI), isolate organic phase and remove organic solvent, and under 100 to 240 ℃ temperature, carry out polyreaction.
3. according to the purposes of claim 1, it is characterized by, described compound (V) and (VI) with 1: 1 to 1: 2.9 is preferably with 1: 2 to 1: 2.5 mol ratio pre-mixing.
4. according to the purposes of claim 1, it is characterized by, described phase-transfer catalyst is a polyoxyethylene glycol.
5. according to the purposes of claim 1, it is characterized by, used inert organic solvents is a dimethylbenzene.
6. according to the purposes of claim 1, it is characterized by, described inert organic solvents uses with 2: 1 to 1: 5 ratio, with respect to compound (VI).
7. according to the purposes of claim 5, it is characterized by, described inert organic solvents is with 2: 1 to 1: 3, preferably uses with 2: 1 to 1: 2 ratio, with respect to compound (VI).
8. according to the purposes of claim 1, it is characterized by, described alkali metal hydroxide is a sodium hydroxide, and is to use with solid form or with aqueous solution form.
9. according to the purposes of claim 1, it is characterized by, alkali metal hydroxide is in 9: 1 to 1: 9 scope to the ratio of water in the described aqueous solution.
10. according to the purposes of claim 9, it is characterized by, alkali metal hydroxide is 2: 3 to 4: 1 to the ratio of water in the described aqueous solution, preferably in 1: 1 to 7: 3 scope.
11. the purposes according to claim 1 is characterized by, described reaction is at 40 to 120 ℃, preferably carries out under 60 to 90 ℃ temperature.
12. the purposes according to claim 1 is characterized by, excessive epihalohydrin (VI) and inert organic solvents are removed by distillation.
13. the purposes according to claim 1 is characterized by, described polyreaction is preferably carried out under 150 to 200 ℃ temperature at 120 to 220 ℃.
14. the purposes according to claim 1 is characterized by, described polyreaction is under reduced pressure carried out.
15. the purposes according to claim 1 is characterized by, the compound of formula V is 2,2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo two spiral shells [5.1.11.2] heneicosane hydrochloride.
16. the purposes according to claim 1 is characterized by, the compound of formula (VI) is an Epicholorohydrin.
17. contain following general formula (I), (II) and (III) synergistic stabilizer mixture of component as the purposes of concentration at the masterbatch of 2.5 to 60 % by weight (with respect to organic material); It is the 65-95 % by weight that described mixture comprises mark; Be preferably 75 to 94 % by weight; The compound of 85 to 94 % by weight (I) particularly; Mark is 5 to 35 % by weight; Be preferably 5 to 20 % by weight; The compound of 5 to 12 % by weight (II) particularly; And mark is 0 to 10 % by weight; Be preferably 1 to 5 % by weight; The compound of 1 to 3 % by weight (III) particularly
Wherein
N and m represent 0 to 100 number independently of each other, but both can not be 0,
R
1Expression hydrogen, C
5-C
7Cycloalkyl or C
1-C
12Alkyl,
R
2And R
3Represent hydrogen atom independently of each other, C
1-C
18Alkyl, or constitute 5 to 13 yuan of rings with the carbon atom that connects them, perhaps with the group of the carbon atom constitutional formula (IV) that they are bonded together,
R
4And R
5Represent hydrogen or C independently of each other
1-C
22Alkyl, oxyradical O
*,-OH ,-NO ,-CH
2CN, benzyl, allyl group, C
1-C
30Alkoxyl group, C
5-C
12Cycloalkyloxy, C
6-C
10Aryloxy (wherein aryl also can further be substituted), C
7-C
20Alkoxy aryl (wherein aryl also can further be substituted), C
3-C
10Alkenyl, C
3-C
6Alkynyl, C
1-C
10Acyl group, halogen or the phenyl that is unsubstituted or through C
1-C
4The phenyl that alkyl replaces,
It is characterized by, in phase transfer reaction, the compound of formula V
, R wherein
1, R
2, R
3And R
4As defined above, and R
6 -The negatively charged ion of expression protonic acid is with the epihalohydrin reaction of formula (VI)
, wherein X represents chlorine, bromine or iodine atom, and then carries out polyreaction to prepare described mixture.
18. method according to claim 17, it is characterized by following steps: pre-mixing compound (V), (VI) and phase-transfer catalyst in organic solvent, the solid alkali metal oxyhydroxide or the alkali metal hydroxide aqueous solution that add 4-20 times of molar weight (with respect to compound (V)), under 20-220 ℃ temperature, react, remove excessive epihalohydrin (VI), isolate organic phase and remove organic solvent, and under 100 to 240 ℃ temperature, carry out polyreaction.
19. the method according to claim 17 is characterized by, described compound (V) and (VI) with 1: 1 to 1: 2.9 is preferably with 1: 2 to 1: 2.5 mol ratio pre-mixing.
20. the method according to claim 17 is characterized by, described phase-transfer catalyst is a polyoxyethylene glycol.
21. the method according to claim 17 is characterized by, used inert organic solvents is a dimethylbenzene.
22. the method according to claim 17 is characterized by, described inert organic solvents uses with 2: 1 to 1: 5 ratio, with respect to compound (VI).
23. the method according to claim 21 is characterized by, described inert organic solvents is with 2: 1 to 1: 3, preferably uses with 2: 1 to 1: 2 ratio, with respect to compound (VI).
24. the method according to claim 17 is characterized by, described alkali metal hydroxide is a sodium hydroxide, and is to use with solid form or with aqueous solution form.
25. the method according to claim 17 is characterized by, alkali metal hydroxide is in 9: 1 to 1: 9 scope to the ratio of water in the described aqueous solution.
26. the method according to claim 25 is characterized by, alkali metal hydroxide is 2: 3 to 4: 1 to the ratio of water in the described aqueous solution, preferably in 1: 1 to 7: 3 scope.
27. the method according to claim 17 is characterized by, described reaction is at 40 to 120 ℃, preferably carries out under 60 to 90 ℃ temperature.
28. the method according to claim 17 is characterized by, excessive epihalohydrin (VI) and inert organic solvents are removed by distillation.
29. the method according to claim 17 is characterized by, described polyreaction is preferably carried out under 150 to 200 ℃ temperature at 120 to 220 ℃.
30. the method according to claim 17 is characterized by, described polyreaction is under reduced pressure carried out.
31. the method according to claim 17 is characterized by, the compound of formula V is 2,2,4,4-tetramethyl--7-oxa--3,20-diaza-21-oxo two spiral shells [5.1.11.2] heneicosane hydrochloride.
32. the method according to claim 17 is characterized by, the compound of formula (VI) is an Epicholorohydrin.
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| KR100849384B1 (en) | 2005-10-21 | 2008-07-31 | 한국생명공학연구원 | A method for fabricating nanogap and nanogap sensor |
| TWI447154B (en) | 2012-11-27 | 2014-08-01 | Ind Tech Res Inst | Pvc product and method for treating surface thereof |
| KR102316673B1 (en) * | 2016-03-14 | 2021-10-25 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for producing oxymethylene copolymer |
| TW202237726A (en) | 2021-01-12 | 2022-10-01 | 瑞士商克萊瑞特國際股份有限公司 | Stabilizer composition for silyl-modified polymer sealants |
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| GB9100257D0 (en) | 1991-01-07 | 1991-02-20 | Sandoz Ltd | Improvements in or relating to organic compounds |
| GB2044272B (en) | 1979-02-05 | 1983-03-16 | Sandoz Ltd | Stabilising polymers |
| DE3273474D1 (en) | 1981-10-16 | 1986-10-30 | Ciba Geigy Ag | Synergistic mixture of low and high molecular weight polyalkyl piperidines |
| US4863981A (en) | 1986-06-30 | 1989-09-05 | Ciba-Geigy Corporation | Synergistic mixture of stabilizers |
| JP2582385B2 (en) | 1987-12-11 | 1997-02-19 | 旭電化工業株式会社 | Stabilized synthetic resin composition |
| DE3919691A1 (en) | 1989-06-16 | 1990-12-20 | Hoechst Ag | POLYALKYL-1-OXA-DIAZASPIRODECANE POLYMER |
| US5175312A (en) | 1989-08-31 | 1992-12-29 | Ciba-Geigy Corporation | 3-phenylbenzofuran-2-ones |
| JP2803300B2 (en) | 1990-03-14 | 1998-09-24 | 住友化学工業株式会社 | Stabilized polypropylene resin composition |
| TW206220B (en) | 1991-07-01 | 1993-05-21 | Ciba Geigy Ag | |
| US5252643A (en) | 1991-07-01 | 1993-10-12 | Ciba-Geigy Corporation | Thiomethylated benzofuran-2-ones |
| TW260686B (en) | 1992-05-22 | 1995-10-21 | Ciba Geigy | |
| NL9300801A (en) | 1992-05-22 | 1993-12-16 | Ciba Geigy | 3- (ACYLOXYPHENYL) BENZOFURAN-2-ON AS STABILIZERS. |
| GB2267490B (en) | 1992-05-22 | 1995-08-09 | Ciba Geigy Ag | 3-(Carboxymethoxyphenyl)benzofuran-2-one stabilisers |
| GB9211602D0 (en) | 1992-06-02 | 1992-07-15 | Sandoz Ltd | Improvements in or relating to organic compounds |
| TW255902B (en) | 1992-09-23 | 1995-09-01 | Ciba Geigy | |
| MX9305489A (en) | 1992-09-23 | 1994-03-31 | Ciba Geigy Ag | 3- (DIHIDROBENZOFURAN-5-IL) BENZOFURAN-2-ONAS, STABILIZERS. |
| US6077889A (en) | 1993-03-24 | 2000-06-20 | Solvay Engineered Polymers | Light stabilizer packages for partial paint applications |
| DE4405387A1 (en) * | 1994-02-19 | 1995-08-24 | Hoechst Ag | Process for the preparation of polyalkyl-1-oxa-diazaspirodecane compounds |
| DE4423054A1 (en) | 1994-07-01 | 1996-01-04 | Hoechst Ag | Polyalkylpiperidine compounds |
| DE4423055A1 (en) | 1994-07-01 | 1996-01-11 | Hoechst Ag | New spiro-poly:alkyl piperidine cpds. useful for improved properties |
| TW358820B (en) | 1995-04-11 | 1999-05-21 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
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| DE19735255B4 (en) | 1997-08-14 | 2007-08-23 | Clariant Produkte (Deutschland) Gmbh | Synergistic stabilizer mixture based on polyalkyl-1-oxa-diazaspirodecane compounds and its use |
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2002
- 2002-02-06 DE DE10204690A patent/DE10204690A1/en not_active Withdrawn
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2003
- 2003-01-29 TW TW092102000A patent/TWI306892B/en not_active IP Right Cessation
- 2003-02-04 DE DE60305003T patent/DE60305003T2/en not_active Expired - Lifetime
- 2003-02-04 JP JP2003566086A patent/JP2005517065A/en active Pending
- 2003-02-04 ES ES03700448T patent/ES2262967T3/en not_active Expired - Lifetime
- 2003-02-04 CN CN201010157779A patent/CN101824163A/en active Pending
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- 2003-02-04 US US10/504,118 patent/US7297734B2/en not_active Expired - Lifetime
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- 2003-02-04 CN CN038021994A patent/CN1615335B/en not_active Expired - Lifetime
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- 2003-02-04 KR KR1020047012245A patent/KR100944297B1/en active IP Right Grant
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114144458A (en) * | 2019-07-10 | 2022-03-04 | 科莱恩国际有限公司 | Stabilizer composition for silyl-modified polymeric sealants |
| CN114144458B (en) * | 2019-07-10 | 2023-11-10 | 科莱恩国际有限公司 | Stabilizer composition for silyl modified polymeric sealants |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE325159T1 (en) | 2006-06-15 |
| US20050228086A1 (en) | 2005-10-13 |
| DE60305003T2 (en) | 2006-12-21 |
| AU2003201747A1 (en) | 2003-09-02 |
| KR20040082418A (en) | 2004-09-24 |
| EP1474471A1 (en) | 2004-11-10 |
| JP2005517065A (en) | 2005-06-09 |
| KR100944297B1 (en) | 2010-02-24 |
| HK1077838A1 (en) | 2006-02-24 |
| CN1615335A (en) | 2005-05-11 |
| EP1474471B8 (en) | 2006-10-04 |
| DE10204690A1 (en) | 2003-08-07 |
| TWI306892B (en) | 2009-03-01 |
| US7297734B2 (en) | 2007-11-20 |
| DE60305003D1 (en) | 2006-06-08 |
| WO2003066719A1 (en) | 2003-08-14 |
| ES2262967T3 (en) | 2006-12-01 |
| CN1615335B (en) | 2011-06-01 |
| TW200302863A (en) | 2003-08-16 |
| EP1474471B1 (en) | 2006-05-03 |
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